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Title: The Influence of Fe substitution into LaCoO3-Electrocatalysts on Oxygen-Reduction Activity

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [2];  [2];  [3];  [1];  [1];  [4];  [2];  [5];  [3];  [4];  [1]
  1. Oregon State Univ., Corvallis, OR (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. National University of Singapore (Singapore)
  4. Nanyang Technological Univ. (Singapore)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

The development of commercially friendly and stable catalysts for oxygen reduction reaction (ORR) is critical for many energy conversion systems such as fuel cells and metal-air batteries. Many Co-based perovskite oxides such as LaCoO3 have been discovered as the stable and active ORR catalysts, which can be good candidates to replace platinum (Pt). Although researchers have tried substituting various transition metals into the Co-based perovskite catalysts to improve the ORR performance, the influence of substitution on the ORR. mechanism is rarely studied. In this paper, we explore the evolution of ORR mechanism after substituting Fe into LaCoO3, using the combination of X-ray photoelectron spectroscopy, high-resolution X-ray microscopy, X-ray diffraction, surface-sensitive soft X-ray absorption spectroscopy characterization, and electrochemical tests. We observed enhanced catalytic activities and increased electron transfer numbers during the ORR in Co-rich perovskite, which are attributed to the optimized e(g) filling numbers and the stronger hybridization of transition metal 3d and oxygen 2p bands. The discoveries in this paper provide deep insights into the ORR catalysis mechanism on metal oxides and new guidelines for the design of Pt-free ORR catalysts.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
Oregon State Univ., Corvallis, OR (United States); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357
OSTI ID:
1510299
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 6 Vol. 11; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Significantly Improved Cyclability of Conversion‐Type Transition Metal Oxyfluoride Cathodes by Homologous Passivation Layer Reconstruction journal January 2020
In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts journal June 2019
Stabilizing atomic Pt with trapped interstitial F in alloyed PtCo nanosheets for high-performance zinc-air batteries journal January 2020
The Velociprobe: An ultrafast hard X-ray nanoprobe for high-resolution ptychographic imaging journal August 2019
Ultrafast X-ray Absorption Studies of the Structural Dynamics of Molecular and Biological Systems in Solution journal May 2011

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalyst
electronic structure
oxygen reduction reaction
perovskite
x-ray absorption spectroscopy